Ethylene interpolymer products and films

Patent metadata

Field	Value
Publication number	US-11312845-B2
Application number	US-202016826689-A
Country	US
Kind code	B2
Filing date	Mar 23, 2020
Priority date	Nov 7, 2017
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

This disclosure relates to ethylene interpolymer compositions and films prepared therefrom. Specifically: ethylene interpolymer products having: a dimensionless nonlinear rheology network parameter, Δ int. , greater than or equal to 0.01, satisfying 0.01×(Z−50) 0.78 ≤Δ int. ≤0.01×(Z−60) 0.78 inequality wherein Z is a normalized molecular weight defined by
Z = M w M e
where M w and M e are the weight average and entanglement molecular weights, and; a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium. The disclosed ethylene interpolymer products have a melt index from about 0.3 to about 500 dg/minute, a density from about 0.855 to about 0.975 g/cc, a polydispersity,

M w M n ,
from about 1.7 to about 25 and a Composition Distribution Breadth Index (CDBI 50 ) from about 1% to about 98%.

First claim

We claim:

1. An ethylene interpolymer product characterized by:
a) a network parameter, Δ int , defined by following inequalities,
0.01×( Z− 50) 0.78 ≤Δ int. ≤0.01×( Z− 60) 0.78

0.01≤Δ int. ≤0.07

wherein Z is a normalized molecular weight defined by

Z
=

M
w

M
e

wherein M w is a weight average molecular weight of the said ethylene interpolymer product as measured using conventional size exclusion chromatography and M e is a molecular weight between entanglements of said ethylene interpolymer as defined by

M
e

=

4
5

⁢

ρ
⁢
R
⁢
T
⁢

m
b
3.49

2
⁢
4
⁢
8
⁢
2
⁢
0

wherein ρ is the melt-state density having a value of 0.780 g/cm 3 at absolute temperature T having a value of 463.15 Kelvin, R is the gas constant having a value of 8.314 J/(mol.Kelvin), M b is the molecular weight per backbone bond calculated in units of g/mol as follows:

M
b

=

n
c

⁢

M

w
/
c

+

2
⁢
8
⁢

(

1
-

n
c

)

2

where n c is the comonomer content in mole fraction determined by Fourier transform infrared (FTIR) spectroscopy according to ASTM D6645-01 (2001) and M w/c is the molecular weight of the comonomer; and
b) a residual catalytic metal of from ≥0.03 to ≤5 ppm of hafnium, wherein said residual catalytic metal is measured using neutron activation,
wherein the ethylene interpolymer product comprises a first ethylene interpolymer, a second ethylene interpolymer and optionally a third ethylene interpolymer, and
wherein the first ethylene interpolymer has a melt index from 0.01 to 200 dg/minute and a density from 0.855 g/cc to 0.975 glee; the second ethylene interpolymer has melt index from 0.3 to 1000 dg/minute and a density from 0.855 g/cc to 0.975 glee; and the third ethylene interpolymer has a melt index from 0.4 to 2000 dg/minute and a density from 0.855 g/cc to 0.975 g/cc.

2. The ethylene interpolymer product of claim 1 , having a dimensionless unsaturation ratio, UR, of from ≥−0.40 to ≤0.06, where UR is defined by the following relationship:
UR=SC U −T U /T U
wherein, SC U is the amount of a side chain unsaturation per 100 carbons and T U is amount of a terminal unsaturation per 100 carbons, in said ethylene interpolymer product, as determined by ASTM D3124-98 and ASTM D6248-98.

3. The ethylene interpolymer product of claim 1 , having a melt index from 0.3 to 500 dg/minute and a density from 0.855 to 0.975 g/cc; wherein melt index is measured according to ASTM D1238 (2.16 kg load and 190° C.) and density is measured according to ASTM D792.

4. The ethylene interpolymer product of claim 1 further comprising up to 25 mole percent of one or more α-olefin units.

5. The ethylene interpolymer product of claim 4 , wherein said one or more α-olefins are C 3 to C 10 α-olefins.

6. The ethylene interpolymer product of claim 5 , wherein said one or more α-olefins are 1-hexene, 1-octene or a mixture of 1-hexene and 1-octene.

7. The ethylene interpolymer product of claim 1 , having a polydispersity, M w /M n , from 1.7 to 25, wherein the weight average molecular weight, M w , and the number average molecular weight, M n , are measured using size exclusion chromatography.

8. The ethylene interpolymer product of claim 1 , having a CDBI 50 from 1% to 98%, wherein CDBI 50 is measured using CTREF.

9. The ethylene interpolymer product of claim 1 , manufactured in a solution polymerization process.

10. The ethylene interpolymer product of claim 1 , synthesized in the presence of at least one homogeneous catalyst formulation.

11. The ethylene interpolymer product of claim 10 , wherein said homogeneous catalyst formulation is a bridged metallocene catalyst formulation comprises a component A defined by Formula (I)

wherein M is hafnium;
G is the element carbon, silicon, germanium, tin or lead;
X represents a halogen atom,
R 6 groups are independently selected from a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical or a C 6-10 aryl oxide radical, these radicals are linear, branched or cyclic or further substituted with halogen atoms, C 1-10 alkyl radicals, C 1-10 alkoxy radicals, C 6-10 aryl or aryloxy radicals;
R 1 represents a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, a C 6-10 aryl oxide radical or alkylsilyl radicals containing at least one silicon atom and C 3-30 carbon atoms;
R 2 and R 3 are independently selected from a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical, a C 6-10 aryl oxide radical or alkylsilyl radicals containing at least one silicon atom and C 3-30 carbon atoms, and;
R 4 and R 5 are independently selected from a hydrogen atom, a C 1-20 hydrocarbyl radical, a C 1-20 alkoxy radical a C 6-10 aryl oxide radical, or alkylsilyl radicals containing at least one silicon atom and C 3-30 carbon atoms.

Assignees

• Nova Chem Int Sa

Inventors

• Sadeghi Soheil
• Sibtain Fazle
• Zhang Zengrong
• Kazemi Niousha
• Kleczek Monika
• Konaganti Vinod
• Gillon Bronwyn
• Goyal Shivendra
• Kasiri Sepideh
• Salomons Stephen
• Taylor Kenneth
• Keshtkar Mehdi

Classifications

• B32B27/327

  comprising polyolefins obtained by a metallocene or single-site catalyst · CPC title

• B32B27/32

  comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)} · CPC title

• B32B27/34

  comprising polyamides · CPC title

• B32B2250/05

  5 or more layers · CPC title

• B32B2307/54

  Yield strength; Tensile strength · CPC title